Production of acyclic condensation products of acetylene



Patented May 2, 1944 UNITED sTATes PATENT I OFFICE PRODUCTION OF ACYCLIC CONDENSATION PRODUCTS or Acn'rYLENE Hanns Peter Staudlngcr, Ewell, and Karl Heinrich Walter Tuerck, Banstead, England, assignors to The Distillers Company Limited, Edinburgh, Scotland, a British company $10 Drawing. Application January 22, 1941, Se-

:ga1loNo. 375,538. In Great Britain January 6,

3 Claims. (Cl. 260 483) This invention is for improvements in or relating to the,production of acyclic condensation products of acetylene.

It has already been shown that acetylene will react rexothermically with ethyl aceto-acetate to give products which consist mainly of cyclic com-,

for the manufacture of acyclic compounds of acetoacetic ester by reacting acetylene with an acetoacetic ester compound of the general formular CHaCO-CHRr-COORz wherein R1 is selected from the group consisting of hydrogen, alkyl and aryl groups and R2 is selected from the group consisting of alkyl and aryl groups in the presence of an inorganic mercury salt as catalyst comprises the steps consisting in forming said mercury salt in situ by reacing a mercury com-- pound with not more than a slight excess of an inorganic acid in the presence of said acetoacetic ester compound and passing acetylene into the reaction mixture whilst cooling to maintain the temperature of said reaction mixture below 30 C.

throughout the reaction whereby the formation of cyclic products is substantially completely prevented. The optimum temperature for the reaction varies according to the substances with which acetylene isreacted, and the nature of the catalyst used.. Such optimum temperatures may be determined by preliminary tests carried out at various temperatures, or by allowing the temperature to rise until active reaction takes place,

which is evident by a rapid absorption of acetylene. By reactive methylene groups is meant a methylene group having in the a-position, two electro-negative substituents such as a carbonyl group,-a carboxyl or carbalkoxy group, a nitrile group or an imide group; it will be appreciated that the electro-negative groups may be the same, as in malonic ester and acetyl acetone or may be difi'erent as in acetoacetic ester and cyanoacetic ester.

A feature of the invention consists in that the condensation reaction is carried out at normal or elevated pressure in the presence of catalysts Motion of vinyl esters and vinyl ethers from acetylene. Examples of such catalysts are the mercuric salts of inorganic acids, especially mere curic sulphate which-is advantageously formed in situ. We have also found that it is necessary to have not more than a slight excess of inorganic acid present in the reaction mixture and it may even be advisable to have no excess of inorganic acid present. With a catalyst solution containing an excess of inorganic acid, the temperature must be regulated more carefully than when no excess acid is present. When the product is recovered by distillation it is preferable to neutralise the catalyst before distillation to avoid decomposition.

Example 1 3 grms. of mercuric oxide were heated with 130 grms. of ethyl acetoacetate until the yellow colour changed to white, 1.1 grms. of concentrated sulphuric acid were then added drop by drop so that the white precipitate first Went into solution and then separated out as a flocculent precipitate. Into this mixture acetylene was introduced whilst the whole was agitated continuously. The acetylene was readily absorbed and the reaction mixture was maintained at 13 C. for 3 hours. After neutralising the product with sodium bicarb'onate and filtering oi! the mercuric sludge, the

product was fractionated in vacuo to yield 39.2% of unchanged ethyl acetoacetate ('B, P. 44 C. at 4 mm. pressure) and 60.8% of a fraction, boiling at 48-50 Crat 4 mm. pressure; consisting of ethyl-a-vinyl-acetoacetic ester (or, more correctly perhaps, a-acetyl-vinyl-acetic ethyl ester). No higher boiling compounds were found in the reaction products.

Example 2 In 50 grms. of ethyl ethylacetoacetate were suspended 2 grms. of yellow mercuric oxide, some drops of acetic acid were added (about 1' grm.) and the mixture heated till the yellow colour turned white. 1.0 grm, of concentrated sulphuric acid was then added drop by drop, the mixture was cooled to 15- -20 ,C., acetylene introduced with l a continuous agitation and the temperature maintained at 20 C.; the catalyst was finally neutralised by sodium bicarbonate and whole reaction mixture was filtered. The product was then dis tilled under 7 mm. pressure and 50% of the distillate obtained consisted of unchanged ethyl which have been already described for the proethylacetoacetate and about 44.4% was a fraction boiling at IO-73 C. containing 94.6% of the condensation product of acetylene with ethyl ethylacetoacetate, namely ethyl-a-vinyl-ethylace- 2. In the process for the manufacture oi acyclic compounds 01 acetcacetic ester by reacting acetylene with an acetcacetic ester compound of the general formula CHaCO CHRI 000R: wherein R1 is selected from the group consisting of hydrogen and alkyl and R2 is alkyl in the presence of an inorganic mercury salt as catalyst the steps consisting in forming said mercury salt in situ by reacting a mercury compound with not more than a slight excess of aninorganic acid in the presence or said acetoacetic ester compound and passing acetylene into the reaction mixture whilst cooling to maintain the temperature of said reaction mixture below 30 .0. throughout the reaction whereby the formation or cyclic products is substantially completely prevented.

3. As new compositions of matter, acyclic 0:- vinyl acetoacetic ester compounds of the general formula CHaCO-CR1(CH=CH2)COOR2 wherein R1 is selected from. the group consisting of hy-- drogen and alkyl and R2 is alkyl.

HANNS PETER STAUDINGER.

i 1 ill ICH WALTER TUERCK. 

